New secondary disazo dyes



Patented May 6, 1930 UNITED STATESHPATENT OFFICE JAMES BADDILEY, PERCY OHORLEY; AND RAIN ALI) BRIGHTMAN, OF BLAGKLEY, HAN- CHESTER, ENGLAND, ASSIGNOBS TO BRITISH DYESTUFFS CORPORATION LIMITED,

03' IBLACKLEY, MANCHESTER, ENGLAND NEW snoounamz nrsazo miss an nrawm Application filed Kay 21, 1927, Serial No. 193,376, and in Great Britain September a, 1926.

In our invention new secondary disazo dyes are prepared by coupling diazotized aminoazo compounds, (includin their homologues and the sulphonic or car oxylic acids 6 thereof in this term) in alkaline or acid media, with 2 :amino-8-naphthol sulphonic acids of the type H wherein R represents a benzene or na hthalene residue which may or may not be urther substituted and R represents a coupled 2- amino-B-naphthol sulphonic acid of the type on a free from amino substituent. We have found that dyestuffs of this characteristic type generally possess the valuable property of yeing regenerated silks, such as viscose silk, in even level shades.

The aminoazo compounds We use may be preparedby coupling any aromatic amines, their substitution products and sulphonic or components, or from unsubstituted aromatic aminoazo compounds by substitution in the known ways. For example, we may use aminoazobenzene' sulphonic acid, or the com- 1-naphthylamine-6- or 7-sulphonic acid, or the compoundobtained by coupl ngl 2-naphthylamine-4: 8-disulphonic acid wit 'l-naphthylamine, and so forth.

wherein It, represents analkyl or acyl group or a benzene or naphthalene residue which are carboxylic acids thereof with suitable middle pound obtained by coupling aniline with- The invention is illustrated by the followmg examples, which, it is understood, are by no means limitative; the parts being by we1ght:--

Ewample 1 343 parts of 2-meta-xylylamino-8-naphthol-G-sulphonic acid are dissolved in water with 500 parts of sodium carbonate. The

solution is cooled and stirred and there is added the diazo suspension. obtainedin the usual way by diazotizing the amino-azo d estufi prepared by coupling 93 parts of aniline with 223 parts of a technical mixture of a-naphthylamine-fiand 7 -sulphonic acids according to known procedure. The mixture is maintained alkaline and stirred until coupling is complete, when it is heated up and .the dyestufi' isolated by the addition of salt. It dyes viscose silk a blue-black shade. The constitution of the dye so obtained is probabl represented, in the form of its sodium sa t, by the formula coma I i -NH.0;H0

Ewample 2 The aminoazo compound obtained by diazotizing 173 parts of metanilic acid and combining with 143 parts of a-naphthylamine in the usual way is diazotized with 250 parts of 36 per cent hydrochloric acid and 69 parts of sodium nitrite and the suspension of diazocompound is stirred into a solution of 337 parts of the sodium salt of 2-phenylamino-8- naphthOl-G-sulphonic acid containing 370 parts-of sodium carbonate. The mixture is maintained alkaline and stirred until coupling is complete, when it is heated up and the dyestuii' precipitated with common salt.

SOINB O H N= N=N N H. CaHu BOaNB Ewamzile a 153 parts of aminosalicylic acid obtained on reduction of the technicalmixture of nitrosalicylic acids are diazotized and combined in the usual manner. with 143-parts of solution of 337 parts of the sodium salt of 2-phenylamino-8-naphthol-6-sulphonic acid. The mixture, which is acid to Congo red P p when it is made alkaline, heated, and the dyestuff isolated by the addition of common salt. It dyes viscose silk a brown shade. If the coupling is performed in an alkaline medium, a different dyestufi is produced. This also dyes viscose silk a brown shade. The constitution of the dye so obtained is probably represented, in the form of its sodium salt, by the formula a-naphthylamine. The resulting aininoazo compound is diazotized in the known manner SOaNa- Our invention is further illustrated by the examples quoted in the following table Disazo colour irom: Shade oixli viscose s Aminoazo compound diazotized- Z-amino-S-naphthol sulphonic acid m-filidine sulphonic acid m-amino-p-cresolmethyl 2-phenylamino-8napthol-6sulphonic acid vi l mfla k e at Aminosaiicylic acid-m-naphthylamine s-hydroxy-2-2-dinaphthylamine-aze-dlsulphonic acid Blue-black Aminosalicylic acid-wi-naphtliylamine 2-pl1enylamino-8-naphthol-6-sulphon c ac d Bl k Aminoazobenzene 2-pheny1annno-8-naphthol-6-su1phon c ac d Brown p-aminoazobenzene-p-carboxylic acid zphenylamino-s-na hthol-6, sulphomc acid Brown p-aminoazobenzene-p-sulphonic acid 8- ydroxy-2-2'dinap thylammo-fi-sulphomc acid Brown p-aminoazobenzene-p-sulphonic acid 2-o-methoxypheny1ammo- 8-n hthol-fi-sulphomc acid Brown p-aminoazobenzene-p-sulphonic acid 2-(2:4-dinitro)"phenylammo-8-naphthol-6-sulphonic acid Red-brown paminoazobenzene-p'-sulphonic acid 2-ethylamino-8-naphthol-6-sulphon1c acid Olive-brown p-aminoazobenzene-p-snlplionic acid 2-benzoylamino-8-naphthoi-6-sulphonic acid Br w p-aminoazobenzene-p-sulphonic acid z-acetylamino-fs-naphthol-Q-sul ohomc ac d Red-brown p-aminoazobenzene-p-sulphonic acid 8-hydroxyr2-naphthyl-giycme-( -suipl ionic acid Orange-brown 2-naphthy1amine=4: 8-disulplionic acid-mnaphthylamine 2-phenylamino-S-naphthol-dsuphon c ac d Navy-blue Aniline 1-naphthyiamine-e-sulphonic acid 2-phenylamino-8-naphtho1esu.phonic acid Blue-black with 69 parts of sodium nitrite and 250 parts of 36 per cent hydrochloric acid, and the susension of diazo-compound is slowly stirred lnto a Well-cooled solution of 2-benzoylamino- 8-naphthol-6-sulphonic acid, containing Sllfllcient sodium carbonate to keep the mixture faintly alkaline throughout. When combination is complete, the mixture is heated up and the dyestufi isolated by the addition of common salt. It gives a deep blue shade on viscose silk. The constitution of the dye so obtained is probablyrepresented, in the form of its sodium salt, by the formula Emample 4 277 parts of para-aminoa'zobenzene sulphonic acid are diazotized in the usual way 'with250 parts of 36 per cent hydrochloric What we claim and desire to secure by Letters Patent is p 1. As new secondary disazo dyes suitable for dyeing regenerated cellulose in even level shades, the dyestufis having the formula R-N=N-R'N=N-Ra wherein R represents a benzene or naphthalene residue free from hydroxyl groups and R represents a coupled 2-amino-8-naphthol sulphonic acid of the type wherein. R represents alkyl or acyl group or benzene or naphthalene residue which are free from amino substituents, the said dyestufi' dyeing regenerated cellulose in even level shades. r

2. As new secondary disazo dyes suitable for dyeing regenerated cellulose in even level shades, the dyestuffs having the formula ,RN=N-R-N=NRa M, in which R represents a benzene or naphthais stirred until coupling is complete,

lene residue and R, represents a coupled 2- amino-S-naphthol sulphonic acid of the type wherein R represents alkyl group or benzene or naphthalene residue which are free from v i O wherein R represents alkyl or acyl group or benzene or naphthalene residue ,which are free from amino substituents, the saiddyestufi dyeing regenerated cellulose in even level shades.

- 4. As new secondary disazo dyes suitable for dyeing regenerated cellulose in even level shades, the dyestuffs having the formula 1 R:N==NRN=N-R;

wherein R represents a benzene residue convtaming a sulphomc or carboxyhc group, R

represents a benzene or naphthalene residue wherein R represents a benzene or naphthalene residue and R represents a benzene or na hthalene residue whlch is free from ammo su stituent, the said dyestuif dyeing regenerv ated cellulose in even level shades.

6. As a new secondary disazo dye suitable 1 for dyeing regenerated cellulose-in even level shade, a dyestufl Inula and being a black powder dissolving in water to give a dark brown solution; addition of dilute mineral acids to this solution producing a reddish shade with a deposition of a brown precipitate, addition of dilute'caustic soda causing the solution to become greenish, the dyestutf dissolving in concentrated sulphuric acid to a bright greenish-blue solution yielding on dilution with water a brown paraphenylene-diamine sulphanilic. acid and 7- amino-2-phenylamino-8-naphthol-6-sulphonic acid, the said dyestuif dyeing regenerated cellulose in even level brown shade.

.In testimony whereof we afiixou'r signaturesa JAMES BADDILEY. PEROYCHORLEY.

RAINALD BRIGHTMAN.

and R represents a 2-amino-8-naphthol sulphonic acld of the type on V H, v

Ik-Jh wherein R represents alkyl group or benzene or naphthalene residue which are free from amino substituents and in which at least one sulphonic acid group is" connected to the 2- .amino-8-naphthol nucleus in the sixth position, the said dyestufi dyeing regenerated cellulose in even level shades.

5. As new secondar disazo dyes suitable for dyeing regenerate cellulose in even level shades, the dyestufis having the formula V on h g the probable for-' i 

